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WO1999026714A1 - Procede de reduction du taux de so2 dans des gaz residuaires emis lors de procedes de desulfuration mis en oeuvre dans des centrales thermiques par voie humide au moyen de chaux ou de calcaire - Google Patents

Procede de reduction du taux de so2 dans des gaz residuaires emis lors de procedes de desulfuration mis en oeuvre dans des centrales thermiques par voie humide au moyen de chaux ou de calcaire Download PDF

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Publication number
WO1999026714A1
WO1999026714A1 PCT/US1998/023669 US9823669W WO9926714A1 WO 1999026714 A1 WO1999026714 A1 WO 1999026714A1 US 9823669 W US9823669 W US 9823669W WO 9926714 A1 WO9926714 A1 WO 9926714A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid sorbent
sulfur oxides
sulfur
limestone
sorbent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1998/023669
Other languages
English (en)
Inventor
David Lee Johnson
Khushrav Erach Nariman
David Lawrence Stern
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
Original Assignee
Mobil Oil AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil AS filed Critical Mobil Oil AS
Priority to EP98957636A priority Critical patent/EP1064079A4/fr
Priority to AU13846/99A priority patent/AU735076B2/en
Priority to CA002311663A priority patent/CA2311663A1/fr
Priority to JP2000521908A priority patent/JP2001523564A/ja
Publication of WO1999026714A1 publication Critical patent/WO1999026714A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/60—Isolation of sulfur dioxide from gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • This invention describes a process for the scrubbing of sulfur oxides, using a solid sorbent such as a magnesium aluminate spinel, from the effluent of conventional wet lime/ limestone SOx reduction processes in coal or oil-fired plants.
  • elemental sulfur is produced by reacting H S and S0 2 in the presence of a catalyst.
  • the Ciaus system uses a combustion chamber which, at 950° to
  • MOST metal oxides
  • This application discloses a process for the scrubbing of sulfur oxides from the effluent of conventional wet lime/limestone SOx reduction processes in coal or oil-fired plants.
  • the sulfur oxides are oxidatively sorted onto magnesium aluminate spinel as solid sorbent. Reduction with the appropriate reducing gases (such as hydrogen) regenerates the catalyst, also yielding a process stream concentrated in SOx.
  • This concentrated SOx stream can then be re-fed to the front end of the coal or oil-fired plants, with the SOx thus produced ultimately being removed in the conventional wet scrubbing technology.
  • This process is capable of capturing >99% of the SOx from power plants, a significant advantage over commercial wet lime/ limestone processes alone, where only 90% of the SOx can be removed, and may allow for the use of high sulfur fuels (having a sulfur content of 4% or greater) in power plant applications.
  • the concept of utilizing the Claus reaction for the conversion of S0 2 to elemental sulfur in power plant applications is known. To the best of our knowledge, however, this is the first example of technology whereby sulfur oxides can be reduced to very low levels following conventional power plant scrubbing technology.
  • Solid, regenerable SOx sorbents show promise for controlling these acid rain precursors by scrubbing these environmental contaminants prior to their release in the atmosphere.
  • a fuel such as coal or oil is bumed in the burner (1) to provide the energy input necessary ultimately for power generation.
  • Approximately 90% of the SOx thus produced is then removed (2) via conventional wet lime/limestone scrubbing technology (3) such as that disclosed in U.S. Patent No. 5,298,473.
  • the residual SOx in the effluent (tailgas) from this wet scrubbing process is oxidatively sorbed onto a solid sorbent located within an absorber (4), preferably a magnesium aluminate spinel as described in U.S. Patent No. 5,229,091
  • the sulfated sorbent in the absorber is then reduced (5) to regenerate the sorbent and to desorb primarily sulfur oxides.
  • Reductants for this process could include hydrogen, CO, C 1 to C 5 hydrocarbons, H 2 S, and other reducing gases. Hydrogen is preferred, however.
  • the offgas is then re-fed to the burner (6) where all sulfur species are converted to S0 2 .
  • the conventional wet scrubbing process will ultimately remove the sulfur oxides, which are recycled to extinction.
  • the use of a sorbent system i.e., MOST in which >99.9% of the SOx can be removed, is key in further reducing sulfur oxide emissions from a power plant facility.
  • the solid sorbents can be impregnated or otherwise coated with an oxidizing catalyst or promoter that promotes the removal of nitrogen oxides and the oxidation of S0 2 to S0 3 in the presence of oxygen. It is believed that S0 3 is more readily adsorbed than S0 2 .
  • One useful catalyst is ceria (cerium oxide).
  • Another useful catalyst is platinum.
  • Other catalytic metals, both free and in a combined form, preferably as an oxide form, can be used, either alone or in combination with each other or in combination with ceria and/or alumina, such as rare earth metals, metals from Group 8 of the Periodic Table, chromium, vanadium, rhenium, tungsten, silver, and combinations thereof.
  • the sulfur oxide-capturing absorbent can be in the form of balls, pebbles, spheres, extrudates, channeled monoliths, microspheres or pellets.
  • the absorber containing the solid sorbent It is preferred to operate the absorber containing the solid sorbent at a temperature from 482° to 760°C (900° to 1400°F). A temperature of from 593° to 704°C (1100° to 1300°F) is most preferred.
  • Oxygen should be introduced into absorber in an amount of from 0.10 to 10 vol.%. Two to 4 vol.% is preferred, however.
  • Pressure within the absorber should be maintained at a pressure of from 500 to 20,000 GHSV. Three thousand to 5,000 GHSV is preferred.
  • An additional benefit of operating the absorber within these parameters is that any carbon monoxide therein is converted into carbon dioxide which is released into the environment. Other gases released from the absorber include nitrogen, oxygen, and trace amounts of sulfur dioxide along with water.
  • the operating parameters for the regeneration of the sorbent are equally applicable to both fluidized and fixed bed processes. Initially a GHSV of 300 should be used when commencing regeneration of the fixed bed absorbent so that a higher concentration of liberated gases can be removed from the regenerator. As regeneration proceeds, the GHSV can be reduced to 50 as the concentration of liberated gases diminishes. Substantially improved regeneration results are anticipated when water is co-fed into the regenerator along with the hydrocarbons. Once regeneration is completed, liberated sulfur dioxide, hydrogen sulfide, and water are recycled to the burner.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un procédé d'élimination des oxydes de soufre (2) de l'effluent issu des procédés (3) traditionnels de réduction d'oxydes de soufre par voie humide au moyen de chaux ou de calcaire, lesquels procédés sont mis en oeuvre dans des centrales thermiques (1) alimentées au charbon ou au mazout. Des absorbants solides (4), tels qu'un spinelle d 'aluminate de magnésium, absorbent les oxydes de soufre par oxydation. Une réduction par des gaz réducteurs appropriés (tels que l'hydrogène) régénère l'absorbant solide (5), ce qui a également pour effet de produire un courant de traitement contenant des oxydes de soufre. Ce courant contenant des oxydes de soufre (6) peut-être réintroduit dans le brûleur des centrales thermiques (1) alimentées au charbon ou au mazout, et les oxydes de soufre ainsi obtenus sont finalement éliminés selon la technique traditionnelle de lavage par voie humide. Ce procédé est susceptible de permettre l'utilisation de combustibles à haute teneur en soufre.
PCT/US1998/023669 1997-11-25 1998-11-06 Procede de reduction du taux de so2 dans des gaz residuaires emis lors de procedes de desulfuration mis en oeuvre dans des centrales thermiques par voie humide au moyen de chaux ou de calcaire Ceased WO1999026714A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98957636A EP1064079A4 (fr) 1997-11-25 1998-11-06 Procede de reduction du taux de so 2? dans des gaz residuaires emis lors de procedes de desulfuration mis en oeuvre dans des centrales thermiques par voie humide au moyen de chaux ou de calcaire
AU13846/99A AU735076B2 (en) 1997-11-25 1998-11-06 Process for the reduction of so2 from wet lime/limestone tailgas in power plant desulfurization processes
CA002311663A CA2311663A1 (fr) 1997-11-25 1998-11-06 Procede de reduction du taux de so2 dans des gaz residuaires emis lors de procedes de desulfuration mis en oeuvre dans des centrales thermiques par voie humide au moyen de chaux ou de calcaire
JP2000521908A JP2001523564A (ja) 1997-11-25 1998-11-06 発電プラント脱硫処理において湿式石灰／石灰石テールガスからｓｏ２を減少させる方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/978,249 US6027704A (en) 1997-11-25 1997-11-25 Process for the reduction of SO2 from wet lime/limestone tailgas in power plant desulfurization processes
US08/978,249 1997-11-25

Publications (1)

Publication Number Publication Date
WO1999026714A1 true WO1999026714A1 (fr) 1999-06-03

Family

ID=25525902

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/023669 Ceased WO1999026714A1 (fr) 1997-11-25 1998-11-06 Procede de reduction du taux de so2 dans des gaz residuaires emis lors de procedes de desulfuration mis en oeuvre dans des centrales thermiques par voie humide au moyen de chaux ou de calcaire

Country Status (6)

Country Link
US (1) US6027704A (fr)
EP (1) EP1064079A4 (fr)
JP (1) JP2001523564A (fr)
AU (1) AU735076B2 (fr)
CA (1) CA2311663A1 (fr)
WO (1) WO1999026714A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7347929B2 (en) 2003-12-05 2008-03-25 Intercat, Inc. Gasoline sulfur reduction using hydrotalcite like compounds
US7361319B2 (en) 2003-12-05 2008-04-22 Intercat, Inc. Mixed metal oxide sorbents
US7361264B2 (en) 2004-06-02 2008-04-22 Intercat, Inc. Mixed metal oxide additives
CN103406020A (zh) * 2013-03-01 2013-11-27 华北电力大学（保定） 用于烟气脱硫脱硝的添加剂及一种烟气脱硫脱硝的方法
US9504957B2 (en) 2014-01-06 2016-11-29 University Of Kentucky Research Foundation Flue gas desulfurization apparatus
US9957284B2 (en) 2014-01-10 2018-05-01 University Of Kentucky Research Foundation Method of increasing mass transfer rate of acid gas scrubbing solvents

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100494135B1 (ko) * 2000-12-05 2005-06-10 주식회사 포스코 화성 테일가스 처리방법
TW200404024A (en) * 2002-08-13 2004-03-16 Intercat Inc Flue gas treatments to reduce NOx and CO emissions
US20100135884A1 (en) * 2009-06-26 2010-06-03 Manuela Serban Process for Desulfurization of Hot Fuel Gases
US20100327224A1 (en) * 2009-06-26 2010-12-30 Manuela Serban Compounds for Desulfurization of Hot Fuel Gases

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183908A (en) * 1977-06-24 1980-01-15 Southern California Edison Company Crystalline calcium sulfate dihydrate and process for making same
US5229091A (en) * 1992-04-15 1993-07-20 Mobil Oil Corporation Process for desulfurizing Claus tail-gas
US5283055A (en) * 1988-06-20 1994-02-01 Rhone-Poulenc Chimie Process using novel catalysts for the selective reduction of nitrogen oxides
WO1995003876A1 (fr) * 1993-07-29 1995-02-09 Consejo Superior Investigaciones Cientificas CATALYSEUR POUR L'ELIMINATION DE SOx ET NOx CONTENUS DANS DES GAZ, SPECIALEMENT DES UNITES FCC, ET PROCEDE DE PREPARATION D'UN TEL CATALYSEUR
US5547648A (en) * 1992-04-15 1996-08-20 Mobil Oil Corporation Removing SOx, NOX and CO from flue gases
US5728358A (en) * 1992-04-15 1998-03-17 Mobil Oil Corporation Sox sorbent regeneration

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE501037C2 (sv) * 1993-03-12 1994-10-24 Flaekt Ab Sätt och anordning för rening av rökgas som innehåller klorväte och svaveldioxid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183908A (en) * 1977-06-24 1980-01-15 Southern California Edison Company Crystalline calcium sulfate dihydrate and process for making same
US5283055A (en) * 1988-06-20 1994-02-01 Rhone-Poulenc Chimie Process using novel catalysts for the selective reduction of nitrogen oxides
US5229091A (en) * 1992-04-15 1993-07-20 Mobil Oil Corporation Process for desulfurizing Claus tail-gas
US5547648A (en) * 1992-04-15 1996-08-20 Mobil Oil Corporation Removing SOx, NOX and CO from flue gases
US5728358A (en) * 1992-04-15 1998-03-17 Mobil Oil Corporation Sox sorbent regeneration
WO1995003876A1 (fr) * 1993-07-29 1995-02-09 Consejo Superior Investigaciones Cientificas CATALYSEUR POUR L'ELIMINATION DE SOx ET NOx CONTENUS DANS DES GAZ, SPECIALEMENT DES UNITES FCC, ET PROCEDE DE PREPARATION D'UN TEL CATALYSEUR

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1064079A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7347929B2 (en) 2003-12-05 2008-03-25 Intercat, Inc. Gasoline sulfur reduction using hydrotalcite like compounds
US7361319B2 (en) 2003-12-05 2008-04-22 Intercat, Inc. Mixed metal oxide sorbents
US7361264B2 (en) 2004-06-02 2008-04-22 Intercat, Inc. Mixed metal oxide additives
CN103406020A (zh) * 2013-03-01 2013-11-27 华北电力大学（保定） 用于烟气脱硫脱硝的添加剂及一种烟气脱硫脱硝的方法
US9504957B2 (en) 2014-01-06 2016-11-29 University Of Kentucky Research Foundation Flue gas desulfurization apparatus
US9957284B2 (en) 2014-01-10 2018-05-01 University Of Kentucky Research Foundation Method of increasing mass transfer rate of acid gas scrubbing solvents

Also Published As

Publication number Publication date
EP1064079A1 (fr) 2001-01-03
CA2311663A1 (fr) 1999-06-03
AU735076B2 (en) 2001-06-28
US6027704A (en) 2000-02-22
EP1064079A4 (fr) 2003-01-29
JP2001523564A (ja) 2001-11-27
AU1384699A (en) 1999-06-15

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